CN106785025A - A kind of sulfonic polymeric thing electrolyte and its in-situ preparation method and application - Google Patents
A kind of sulfonic polymeric thing electrolyte and its in-situ preparation method and application Download PDFInfo
- Publication number
- CN106785025A CN106785025A CN201710059631.4A CN201710059631A CN106785025A CN 106785025 A CN106785025 A CN 106785025A CN 201710059631 A CN201710059631 A CN 201710059631A CN 106785025 A CN106785025 A CN 106785025A
- Authority
- CN
- China
- Prior art keywords
- lithium
- sulfonic
- polymer
- polymeric thing
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of sulfonic polymeric thing electrolyte and its in-situ preparation method and application.Preparation method is in dissolving the polymer in solvent, to add the silane coupler containing SH, and film forming after the bubble of ultrasonic removing system is then immersed in oxidizing agent solution, and the SH of end is oxidized into sulfonic group, while silane coupler hydrolysis generation SiO2, acidifying in acid solution is placed into after cleaning, after taking-up, rinsed with deionization, and the acid for removing remnants is boiled with water, placing into during lithium exchanges liquid carries out lithium exchange, and cleaning, drying obtains the polymer dielectric film containing Sulfonic Lithium.The sulfonic polymeric thing electrolyte heat endurance and electrochemical properties of preparation are improved, can be applied in the electrochmical power source system such as lithium ion battery, meet lithium ion battery high current charge-discharge, while obtaining the effect of single ion conductor, improve the security performance of battery.
Description
Technical field
The present invention relates to electrochemical field, more particularly to a kind of sulfonic polymeric thing electrolyte and its in-situ preparation method and
Using.
Background technology
Lithium ion battery have high-energy-density, high power, memory-less effect, it is environment-friendly the features such as, be it is a kind of green
Electrochmical power source, with good portability, be widely used to the mobile digital such as mobile phone, notebook computer, camera product and with
And the field such as the military equipment such as medical supply and unmanned plane such as pacemaker, lung ventilator.However, what lithium ion battery was used
Organic liquid electrolyte causes that lithium ion battery has potential safety hazard, and e.g., the main component of liquid electrolyte is carbonates,
With it is volatile, inflammable, reactivity is high the features such as, therefore the burning even potential safety hazard of blast are there is, and in organic liquor
, it is necessary to add lithium salts for conducting lithium ions in body electrolyte, but in order to improve solubility of the lithium salts in electrolyte, general lithium
Salt all has macroanion, so allows for lithium ion than anion easily solvation, and it is only 0.3 to cause lithium ion transference number
, there are serious polarization phenomena in charging and discharging, therefore potential safety hazard is there is in charging process in left and right.At present, it is main
Solution is to substitute liquid electrolyte using polymer dielectric, is improved by the reactivity etc. for reducing electrolyte and electrode
The security performance of lithium ion battery, and substitute lithium salts raising lithium ion transference number raising lithium ion battery using single ion conductor
Security performance.Inorganic matter is added in polymer dielectric and forms organic inorganic composite polymer electrolyte, it is aobvious due to improving
Write the performances such as raising polymer dielectric and mechanical stability and receive extensive concern, in terms of lithium single ion conductor, with film
Based on upper grafting sulfonic groups.
Can be with adsorptive liquid electrolyte solvent, and containing having abundant in sulfonic polymer body phase in polymer dielectric
Sulfonic Lithium, abundant lithium ion can be dissociateed, it is achieved thereby that the quick conduction of lithium ion.Organic inorganic composite polymer electricity
Solution matter is mainly adds inorganic filler in polymeric matrix, and filler is by the thing with polymer segment formation centered on filler
Reason cross-linked network system, strengthens the ability of polymer dispersive stress, improves the mechanical performance and heat endurance of polymer dielectric.
If sulfonic acid group can be introduced while inorganic filler is filled, can realize containing sulfonic organo-mineral complexing
Polymer dielectric function it is compound, and then lithium single ion conductor polymer film is obtained, so as to improve the comprehensive of polymer dielectric
Close performance.
The content of the invention
The first object of the present invention is to provide a kind of original containing sulfonic organic inorganic composite polymer electrolyte
Position preparation method, comprises the following steps：
1) polymer solution for forming that mass fraction is 5%~30% in solvent is dissolved the polymer in, is added and is contained-SH
The silane coupler of base, the bubble and film forming of ultrasound removing system, obtain the polymer that thickness is 1-100 μm after being well mixed
Film；Wherein described polymer is polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), Kynoar (PVDF), poly- inclined
At least one in viton copolymers (P (VDF-HFP)), the solvent is the good solvent of the polymer；
2) 0.3~6h in the polymer film immersion oxidizing agent solution that will be obtained ,-SH bases are oxidized to-SO in making film3H bases, together
When silane coupler hydrolysis generation SiO2, so as to be contained-SO3The SiO of H bases2Inorganic whisker polymer film, by going
After ion water wash immerse 0.01~12M acid solution in further protonate, then with deionized water drip washing and boil removing it is residual
The acid stayed, obtains sulfonic polymeric thing film；
3) it is 0.01mol L by sulfonic polymeric thing film immersion concentration-1Lithium exchange liquid in carry out lithium exchange, then spend
Ionized water is rinsed and boiled, drying, obtains the sulfonic polymeric thing electrolyte containing Sulfonic Lithium.
Preferably, step 1) in, also including to the inorganic Louis that 0.1-5% mass fractions are added in the polymer solution
This acid is promoting the dissociation of lithium ion；The inorganic lewis acid is selected from nano level alundum (Al2O3) (Al2O3), silica
(SiO2), calcium oxide (CaO), magnesia (MgO), lithium fluoride (LiF), titanium dioxide (TiO2) at least one.
Preferably, step 1) in, the film forming is in being cast in substrate or being scratched, then in 40~100 by mixed solution
0.5~50h is dried under DEG C vacuum condition and stripping group bottom forms the polymer film, wherein the substrate is glass plate or poly- four
PVF plate.
Preferably, step 1) in, the film forming is that mixed solution is obtained into non-woven polymers film by spinning.
Preferably, step 1) in, the good solvent of the polymer is 1-METHYLPYRROLIDONE (NMP) or N, N- dimethyl methyl
Acid amides (DMF).
Preferably, step 2) in, the oxidizing agent solution is hydrogen peroxide (H2O2), nitric acid (HNO3), potassium permanganate
(KMnO4), potassium bichromate (K2Cr2O7) or hypochlorous acid (HClO).
Preferably, step 2) in, the acid solution is at least one in sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid.
Preferably, step 3) in, it is lithium acetate (CH that the lithium exchanges liquid3COOLi), lithium nitrate (LiNO3), lithium sulfate
(Li2SO4), lithium metasilicate (Li2SiO3), at least one water or ethanol solution in lithium hydroxide (LiOH).
The second object of the present invention is to provide the sulfonic polymeric thing electrolyte of above method preparation.
The third object of the present invention is to provide above-mentioned sulfonic polymeric thing electrolyte and changes in lithium ion battery, lithium-sulfur cell etc.
Learn the application of power supply system.The wherein SiO of silane coupler in-situ hydrolysis generation2Used as inorganic filler, its cation can fill
Work as lewis acid, with Li+Competition, instead of Li+There is Lewis Acids and Bases effect with the group such as the O on polymer segment, not only suppress
The recrystallization of polymer, the crystallinity for reducing polymer, in addition, this compete the dissociation for further promoting Li salt, increase
The number of free carrier.And O etc. then serves as lewis base, with lewis acid Li+Interact, form filler Li+It is rich
Phase, and form Li+The new tunnel of migration.Thus obtain conductivity at room temperature and Li higher+Transport number.Therefore, it is in situ raw
Into filler effect mainly by this phase of the realization that interacts of filler and polymer, filler and electrolyte and lithium salts
Interaction can be attributed to a kind of interface behavior.Form the performance that continuous interface is conducive to filler function.Filler/cation
Fu Xiang, boundary is considered as the new tunnel of electrolytic salt cation transport.Research shows that the passage can realize the fast of ion
Speed conduction, so as to obtain conductivity at room temperature and cation transport number higher.The introducing of inorganic filler can also play stabilization
The effect of electrolyte/electrode interface, improves the electrochemical window of electrolyte system.Because inorganic filler can catch remaining in
The water of the impurity in electrolyte, such as oxygen, trace, with guard electrode.Therefore, continuous, effective filler/electrolytic salt is formed
The interface of cation is particularly important for improving the performance of electrolyte system.Furthermore it is preferred that, to improve effect, also can be simultaneously
Inorganic filler is it is possible to additionally incorporate to improve its concentration.
The beneficial effects of the invention are as follows：
1. polymer solution is uniform solution, is well mixed, and the inorganic phase occurred with organic mixed solution point will not occur
Solution phenomenon, the SiO that coupling agent is generated in film situ2Can be distributed more homogeneous.
2. inorganic filler and sulfonic synchronous introducing are realized, and method is simply efficient.Obtained polymer dielectric
Heat endurance, electrochemical properties and the electrochemical properties using the battery of the polymer dielectric are improved.
3. directly use and contain the coupling agent conduct-SO that end group is-SH3H sources, it is to avoid on organic polymer grafting-
SO3The embrittlement of H, it is to avoid in SiO2Grafting-SO3The drawbacks of H grafting rates are too low, can obtain toughness preferably, and containing it is abundant-
SO3The polymer dielectric film of Li.After soaking plasticising using electrolyte solvents such as EC, DMC ,-SO can be made3Li ionizes out abundant
Lithium ion, the polymer dielectric film of high-lithium ion conductance can be obtained, meet lithium ion battery high current charge-discharge, while
The effect of single ion conductor is obtained, the security performance of battery is improved.
4. the in situ of inorganic oxide introduces the heat endurance that can also improve polymer dielectric.
Brief description of the drawings
Fig. 1 is the sulfonic polymeric thing dielectric film of embodiment 2 through the cross-sectional scans electron microscope after liquid nitrogen treatment.
Fig. 2 is the red of the Kynoar without the 3-mercaptopropyi trimethoxy silane-hexafluoropropene film of embodiment 2
Outer absorption spectrogram.
Fig. 3 be embodiment 2 through in 80 DEG C of vacuum drying ovens dry 12 after, the polymer film containing-SH bases for obtaining it is infrared
Absorb spectrogram.
Fig. 4 be embodiment 2 through in vacuum drying oven 60 DEG C drying after, the Inorganic whisker containing Sulfonic Lithium for obtaining
The infrared absorption spectra of sulfonic polymeric thing dielectric film.
Fig. 5 be embodiment 2 through in vacuum drying oven 60 DEG C drying after, the Inorganic whisker containing Sulfonic Lithium for obtaining
The EDS-mapping figures of sulfonic polymeric thing dielectric film.
Specific embodiment
Specific embodiment of the invention is elaborated below in conjunction with embodiment and accompanying drawing.
Embodiment 1
5g Kynoar powder is dissolved in 45g 1-METHYLPYRROLIDONEs, after being completely dissolved, 5g 3- sulfydryls is added
Propyl trimethoxy silicane, after stirring makes its mixing full and uniform, takes the slide that 0.5mL is coated on 25.4mm × 76.2mm
On, it is placed in 80 DEG C of vacuum drying ovens and dries 12h.Obtain final product the polymer film containing-SH bases.
The H of the immersion of the polymer film containing-SH bases 35% that will be prepared2O2In solution, 6h is aoxidized under the conditions of 65 DEG C, together
When make silane hydrolyzate, obtain surface and contain-SO3The SiO of H2Inorganic whisker polymer film, takes out composite polymeric film, spends
Ion water wash three times.0.2M H will be placed in by the composite polymeric film of pretreatment again2SO41h is acidified in solution, deionization is used
Water wash three times, after film be put into water boil 1h.The composite polymeric film of acidifying is placed to 1M CH again3In COOLi solution
Carry out lithium and exchange 12h, deionized water drip washing three times, after film be put into water boil 1h.60 DEG C are put into vacuum drying oven to dry
To the sulfonic polymeric thing dielectric film of the Inorganic whisker containing Sulfonic Lithium.
Embodiment 2
5g Kynoar-hexafluoropropylene copolymer powder is dissolved in 45g 1-METHYLPYRROLIDONEs, is completely dissolved
Afterwards, 5g 3-mercaptopropyi trimethoxy silanes are added, while adding 2g 10%HNO3, to promote 3- mercaptopropyi trimethoxies
The hydrolysis of silane, while playing a part of preliminary oxidation, after stirring makes its mixing full and uniform, takes 0.5mL and is coated on 25.4mm
On the slide of × 76.2mm, under the conditions of 25 DEG C, relative humidity 50%RH, it is placed in 80 DEG C of vacuum drying ovens and dries 12h.Obtain final product
Polymer film containing-SH bases.
The H of the immersion of the polymer film containing-SH bases 35% that will be prepared2O2In solution, 6h is aoxidized under the conditions of 65 DEG C, together
When make silane hydrolyzate, obtain surface and contain-SO3The SiO of H2Inorganic whisker polymer film, takes out composite polymeric film, spends
Ion water wash three times.0.2M H will be placed in by the composite polymeric film of pretreatment again2SO41h is acidified in solution, deionization is used
Water wash three times, after film be put into water boil 1h.The composite polymeric film of acidifying is placed to 1M CH again3In COOLi solution
Carry out lithium and exchange 12h, deionized water drip washing three times, after film be put into water boil 1h.60 DEG C are put into vacuum drying oven to dry
To the sulfonic polymeric thing dielectric film of the Inorganic whisker containing Sulfonic Lithium.
Fig. 1 is obtained sulfonic polymeric thing dielectric film processed through liquid nitrogen after cross-sectional scans electron microscope, therefrom can be with
See that nano silicon is more evenly distributed in the middle of body phase.Fig. 2,3,4 are respectively without 3- mercaptopropyi front threes
The Kynoar of TMOS-hexafluoropropene film, the polymer containing-SH bases obtained after in 80 DEG C of vacuum drying ovens dry 12
The sulfonic polymeric thing dielectric film of film, the Inorganic whisker containing Sulfonic Lithium obtained after 60 DEG C of drying in vacuum drying oven
Infrared absorption spectra, it can be seen that in 976cm after oxidation-1Stronger-SO is occurred in that at wave number3-Absworption peak.Fig. 5 is sulphur
The section mapping of acid-based polymer electrolyte, it can be seen that S, Si, O element on the section of sulfonic polymeric thing electrolyte
It is uniformly distributed, illustrates-SO in film3It is equally distributed.
Sulfonic polymeric thing dielectric film is put into EC/PC (volume ratios 1：1) at least 6h is activated, according to ac impedance spectroscopy,
The electrical conductivity for obtaining the sulfonic polymeric thing dielectric film reaches 1.08 × 10-4S cm-1. lithium ion transference numbers reach 0.92 ±
0.3。
Embodiment 3
5g Kynoar powder is dissolved in 45g 1-METHYLPYRROLIDONEs, after being completely dissolved, 5g 3- sulfydryls is added
Propyl trimethoxy silicane, after adding 1g 100nm alundum (Al2O3)s, stirring to make its mixing full and uniform, takes 0.5mL and is coated on
On the slide of 25.4mm × 76.2mm, it is placed in 80 DEG C of vacuum drying ovens and dries 12h.Obtain final product the polymer film containing-SH bases.
The H of the immersion of the polymer film containing-SH bases 35% that will be prepared2O2In solution, 6h is aoxidized under the conditions of 65 DEG C, together
When make silane hydrolyzate, obtain surface and contain-SO3The SiO of H2Inorganic whisker polymer film, takes out composite polymeric film, spends
Ion water wash three times.0.2M H will be placed in by the composite polymeric film of pretreatment again2SO41h is acidified in solution, deionization is used
Water wash three times, after film be put into water boil 1h.The composite polymeric film of acidifying is placed to 1M CH again3In COOLi solution
Carry out lithium and exchange 12h, deionized water drip washing three times, after film be put into water boil 1h.60 DEG C are put into vacuum drying oven to dry
To the sulfonic polymeric thing dielectric film of the Inorganic whisker containing Sulfonic Lithium.
Sulfonic polymeric thing dielectric film is put into EC/PC (volume ratios 1：1) at least 6h is activated, according to ac impedance spectroscopy,
The electrical conductivity for obtaining the sulfonic polymeric thing dielectric film reaches 3.22 × 10-4S cm-1Lithium ion transference number reach 0.93 ±
0.04。
Embodiment 4
5g Kynoar-hexafluoropropylene copolymer powder is dissolved in 45g 1-METHYLPYRROLIDONEs, is completely dissolved
Afterwards, add 5g 3-mercaptopropyi trimethoxy silanes, stirring make its mixing it is full and uniform after, take 0.5mL be coated on 25.4mm ×
On the slide of 76.2mm, it is placed in 80 DEG C of vacuum drying ovens and dries 12h.Obtain final product the polymer film containing-SH bases.
The H of the immersion of the polymer film containing-SH bases 35% that will be prepared2O2In solution, 6h is aoxidized under the conditions of 65 DEG C, together
When make silane hydrolyzate, obtain surface and contain-SO3The SiO of H2Inorganic whisker polymer film, takes out composite polymeric film, spends
Ion water wash three times.0.2M H will be placed in by the composite polymeric film of pretreatment again2SO41h is acidified in solution, deionization is used
Water wash three times, after film be put into water boil 1h.The composite polymeric film of acidifying is placed to 1M CH again3In COOLi solution
Carry out lithium and exchange 12h, deionized water drip washing three times, after film be put into water boil 1h.60 DEG C are put into vacuum drying oven to dry
To the sulfonic polymeric thing dielectric film of the Inorganic whisker containing Sulfonic Lithium.
Embodiment 5
5g Kynoar-hexafluoropropylene copolymer powder is dissolved in 45g 1-METHYLPYRROLIDONEs, is completely dissolved
Afterwards, 5g 3-mercaptopropyi trimethoxy silanes are added, is stirred after making its mixing full and uniform, the spinning on non-woven fabrics machine is obtained final product
Thickness range is 1-200 μm of the non woven cloth in polymer film containing-SH bases.The non woven cloth in polymer film containing-SH bases that will be prepared
The HNO of immersion 65%3In solution, 1h is aoxidized, while making silane hydrolyzate, obtain surface and contain-SO3The SiO of H2Inorganic whisker
Polymer film, takes out composite polymeric film, with deionized water drip washing three times.Film is put into water afterwards boils 1h.Again by acidifying
Composite polymeric film is placed to 1M CH3Carried out in COOLi solution lithium exchange 12h, deionized water drip washing three times, after film is put into
1h is boiled in water.It is put into vacuum drying oven 60 DEG C and dries the sulfonic polymeric thing electricity for obtaining the Inorganic whisker containing Sulfonic Lithium
Solution plasma membrane.
Embodiment 6
A kind of battery, positive pole uses active material LiCoO2, conductive agent selects acetylene black, and bonding agent is used in embodiment 1
Sulfonic polymeric thing electrolyte, negative pole use active material graphite.
Embodiment 7
A kind of battery, positive pole uses active material LiCoO2, conductive agent selects acetylene black, and bonding agent is used in embodiment 2
Sulfonic polymeric thing electrolyte, negative pole use active material graphite.
Embodiment 8
A kind of battery, positive pole uses active material LiCoO2, conductive agent selects acetylene black, and bonding agent is used in embodiment 3
Sulfonic polymeric thing electrolyte, negative pole use active material graphite.
Embodiment 9
A kind of battery, positive pole uses active material LiCoO2, conductive agent selects acetylene black, and bonding agent is used in embodiment 4
Sulfonic polymeric thing electrolyte, negative pole use active material graphite.
Embodiment 10
A kind of battery, positive pole uses active material LiCoO2, conductive agent selects acetylene black, and bonding agent is used in embodiment 5
Sulfonic polymeric thing electrolyte, negative pole use active material graphite.
Embodiment described above has been described in detail to technical scheme, it should be understood that the above is only
It is specific embodiment of the invention, is not intended to limit the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion replacement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of in-situ preparation method of sulfonic polymeric thing electrolyte, it is characterised in that comprise the following steps：
1) polymer solution for forming that mass fraction is 5%~30% in solvent is dissolved the polymer in, is added containing-SH bases
Silane coupler, removes the bubble and film forming of system after being well mixed, obtain the polymer film that thickness is 1-100 μm；Wherein institute
State polymer be in polymethyl methacrylate, polyacrylonitrile, Kynoar, the propylene copolymer of Kynoar-six extremely
Few one kind, the solvent is the good solvent of the polymer；
2) 0.3~6h in the polymer film immersion oxidizing agent solution that will be obtained ,-SH bases are oxidized to-SO in making film3H bases, while silicon
Alkane coupling agent hydrolysis generation SiO2, so as to be contained-SO3The SiO of H bases2Inorganic whisker polymer film, by deionization
After water wash immerse 0.01~12M acid solution in further protonate, then with deionized water drip washing and boil remove residual
Acid, obtains sulfonic polymeric thing film；
3) it is 0.01-5mol L by sulfonic polymeric thing film immersion concentration-1Lithium exchange liquid in carry out lithium exchange, then spend from
Sub- water is rinsed and boiled, drying, obtains the sulfonic polymeric thing electrolyte containing Sulfonic Lithium.
2. the in-situ preparation method of sulfonic polymeric thing electrolyte according to claim 1, it is characterised in that：Step 1) in,
Also include to the inorganic lewis acid that 0.01-5% mass fractions are added in the polymer solution；The inorganic lewis acid choosing
At least one from nano level alundum (Al2O3), silica, calcium oxide, magnesia, lithium fluoride, titanium dioxide.
3. the in-situ preparation method of sulfonic polymeric thing electrolyte according to claim 1, it is characterised in that：Step 1) in,
The film forming is in being cast in substrate or being scratched, then in 0.5~50h of drying under 40~100 DEG C of vacuum conditions by mixed solution
And stripping group bottom forms the polymer film, wherein the substrate is glass plate or polyfluortetraethylene plate.
4. the in-situ preparation method of sulfonic polymeric thing electrolyte according to claim 1, it is characterised in that：Step 1) in,
The film forming is that mixed solution is obtained into non-woven polymers film by spinning.
5. the in-situ preparation method of sulfonic polymeric thing electrolyte according to claim 1, it is characterised in that：Step 1) in,
The good solvent of the polymer is 1-METHYLPYRROLIDONE or N,N-dimethylformamide.
6. the in-situ preparation method of sulfonic polymeric thing electrolyte according to claim 1, it is characterised in that：Step 2) in,
The oxidizing agent solution is hydrogen peroxide, nitric acid, potassium permanganate, potassium bichromate or hypochlorite solution.
7. the in-situ preparation method of sulfonic polymeric thing electrolyte according to claim 1, it is characterised in that：Step 2) in,
The acid solution is at least one in sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid.
8. the in-situ preparation method of sulfonic polymeric thing electrolyte according to claim 1, it is characterised in that：Step 3) in,
The lithium exchanges liquid at least one water or ethanol in lithium acetate, lithium nitrate, lithium sulfate, lithium metasilicate, lithium hydroxide are molten
Liquid.
9. the sulfonic acid that prepared by the in-situ preparation method of sulfonic polymeric thing electrolyte as described in any one in claim 1~8
Base polymer electrolyte.
10. application of the sulfonic polymeric thing electrolyte in electrochmical power source system described in claim 9, the electrochmical power source includes
Lithium ion battery, lithium-sulfur cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710059631.4A CN106785025B (en) | 2017-01-24 | 2017-01-24 | A kind of sulfonic polymeric object electrolyte and its in-situ preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710059631.4A CN106785025B (en) | 2017-01-24 | 2017-01-24 | A kind of sulfonic polymeric object electrolyte and its in-situ preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106785025A true CN106785025A (en) | 2017-05-31 |
| CN106785025B CN106785025B (en) | 2019-05-03 |
Family
ID=58942193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710059631.4A Active CN106785025B (en) | 2017-01-24 | 2017-01-24 | A kind of sulfonic polymeric object electrolyte and its in-situ preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106785025B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107221704A (en) * | 2017-06-29 | 2017-09-29 | 中国科学院长春应用化学研究所 | A kind of electrolyte for lithium secondary batteries and lithia gas secondary cell |
| CN108091930A (en) * | 2017-12-05 | 2018-05-29 | 厦门大学 | New single-ion polymer electrolyte and preparation method and application |
| CN110212241A (en) * | 2019-06-12 | 2019-09-06 | 哈尔滨工业大学 | A kind of solid electrolyte membrane and its preparation process and application |
| CN110504441A (en) * | 2018-05-17 | 2019-11-26 | 华为技术有限公司 | A kind of modified silicon based anode material and preparation method thereof and lithium ion battery |
| CN110994046A (en) * | 2019-12-04 | 2020-04-10 | 中南大学 | Mixed electrolyte of water-based ion battery |
| CN111224154A (en) * | 2020-02-17 | 2020-06-02 | 中国科学院化学研究所 | Mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and preparation method and application thereof |
| CN111477957A (en) * | 2020-04-22 | 2020-07-31 | 浙江大学 | Lithium metal battery electrolyte containing composite additive and preparation method thereof |
| CN112993384A (en) * | 2021-01-21 | 2021-06-18 | 上海工程技术大学 | In-situ polymerized ZnO composite solid polymer electrolyte and preparation method thereof |
| CN114914508A (en) * | 2022-05-13 | 2022-08-16 | 宿迁时代储能科技有限公司 | Application of porous membrane in neutral water system organic flow battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5161048A (en) * | 1990-12-26 | 1992-11-03 | Ppg Industries, Inc. | Electrochromic window with metal grid counter electrode and acidic polyelectrolyte |
| KR20030075101A (en) * | 2002-03-16 | 2003-09-22 | 한국과학기술연구원 | Gel type polymer electrolyte including leveling agent, lithium metal polymer battery with it, and fabrication method thereof |
| CN101218281A (en) * | 2005-06-09 | 2008-07-09 | 东洋纺织株式会社 | Sulfonic acid group-containing polymer, method for producing same, resin composition containing such sulfonic acid group-containing polymer, polymer electrolyte membrane, polymer electrolyte membrane/ |
| JP2010202866A (en) * | 2009-02-09 | 2010-09-16 | Tokyo Institute Of Technology | Sulfonated polymer and proton conductive membrane using the same |
| CN105899584A (en) * | 2014-01-15 | 2016-08-24 | 庄臣及庄臣视力保护公司 | Polymers comprising sulfonic acid groups |
-
2017
- 2017-01-24 CN CN201710059631.4A patent/CN106785025B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5161048A (en) * | 1990-12-26 | 1992-11-03 | Ppg Industries, Inc. | Electrochromic window with metal grid counter electrode and acidic polyelectrolyte |
| KR20030075101A (en) * | 2002-03-16 | 2003-09-22 | 한국과학기술연구원 | Gel type polymer electrolyte including leveling agent, lithium metal polymer battery with it, and fabrication method thereof |
| CN101218281A (en) * | 2005-06-09 | 2008-07-09 | 东洋纺织株式会社 | Sulfonic acid group-containing polymer, method for producing same, resin composition containing such sulfonic acid group-containing polymer, polymer electrolyte membrane, polymer electrolyte membrane/ |
| JP2010202866A (en) * | 2009-02-09 | 2010-09-16 | Tokyo Institute Of Technology | Sulfonated polymer and proton conductive membrane using the same |
| CN105899584A (en) * | 2014-01-15 | 2016-08-24 | 庄臣及庄臣视力保护公司 | Polymers comprising sulfonic acid groups |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107221704A (en) * | 2017-06-29 | 2017-09-29 | 中国科学院长春应用化学研究所 | A kind of electrolyte for lithium secondary batteries and lithia gas secondary cell |
| CN108091930A (en) * | 2017-12-05 | 2018-05-29 | 厦门大学 | New single-ion polymer electrolyte and preparation method and application |
| CN108091930B (en) * | 2017-12-05 | 2019-10-25 | 厦门大学 | Novel single-ion polymer electrolyte and the preparation method and application thereof |
| CN110504441A (en) * | 2018-05-17 | 2019-11-26 | 华为技术有限公司 | A kind of modified silicon based anode material and preparation method thereof and lithium ion battery |
| CN110504441B (en) * | 2018-05-17 | 2021-06-01 | 华为技术有限公司 | Modified silicon-based negative electrode material, preparation method thereof and lithium ion battery |
| CN110212241A (en) * | 2019-06-12 | 2019-09-06 | 哈尔滨工业大学 | A kind of solid electrolyte membrane and its preparation process and application |
| CN110994046A (en) * | 2019-12-04 | 2020-04-10 | 中南大学 | Mixed electrolyte of water-based ion battery |
| CN111224154A (en) * | 2020-02-17 | 2020-06-02 | 中国科学院化学研究所 | Mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and preparation method and application thereof |
| CN111477957A (en) * | 2020-04-22 | 2020-07-31 | 浙江大学 | Lithium metal battery electrolyte containing composite additive and preparation method thereof |
| CN112993384A (en) * | 2021-01-21 | 2021-06-18 | 上海工程技术大学 | In-situ polymerized ZnO composite solid polymer electrolyte and preparation method thereof |
| CN114914508A (en) * | 2022-05-13 | 2022-08-16 | 宿迁时代储能科技有限公司 | Application of porous membrane in neutral water system organic flow battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106785025B (en) | 2019-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106785025B (en) | A kind of sulfonic polymeric object electrolyte and its in-situ preparation method and application | |
| Xiang et al. | A flame-retardant polymer electrolyte for high performance lithium metal batteries with an expanded operation temperature | |
| Zhang et al. | Polymer electrolytes for high energy density ternary cathode material-based lithium batteries | |
| Yu et al. | Electrode–electrolyte interfaces in lithium-based batteries | |
| CN105932203B (en) | A kind of preparation method of the porosity lithium ion battery separator with inierpeneirating network structure | |
| CN109546207A (en) | A kind of composite solid polymer electrolyte film and its preparation method and application | |
| CN104766946B (en) | Anode slice of lithium ion battery and preparation method thereof and lithium ion battery | |
| JP2016219411A (en) | Lithium metal battery | |
| CN108539122A (en) | A kind of positive plate and the lithium rechargeable battery comprising the positive plate | |
| Li et al. | Improving cyclic stability of lithium nickel manganese oxide cathode for high voltage lithium ion battery by modifying electrode/electrolyte interface with electrolyte additive | |
| JP2001503910A (en) | Highly conductive ion exchange polymers and methods | |
| CN108140875A (en) | Non-aqueous electrolyte secondary battery | |
| CN111786018B (en) | High-voltage polymer electrolyte, high-voltage polymer lithium metal battery and preparation method of battery | |
| CN105633467A (en) | Electrolyte and lithium ion battery adopting same | |
| Xu et al. | A rigid-flexible coupling gel polymer electrolyte towards high safety flexible Li-Ion battery | |
| CN103490040A (en) | Preparation method of lithium titanate-graphene composite material | |
| CN104466183A (en) | Positive electrode material of polypyrrole lithium sulfur battery and preparation method of positive electrode material | |
| CN106684443A (en) | Preparation method for modified graphene oxide-doped solid polymer electrolyte | |
| CN109449376A (en) | A kind of compound metal lithium electrode and preparation method thereof | |
| CN110911741B (en) | Carbon oxide sphere doped solid polymer electrolyte membrane and preparation method and application thereof | |
| Rodriguez et al. | Freestanding polyimide fiber network as thermally safer separator for high-performance Li metal batteries | |
| CN109244370B (en) | Preparation method of secondary lithium metal battery cathode steam protective film | |
| Chagnes | Lithium battery technologies: electrolytes | |
| CN105280868A (en) | Vinylidene fluoride-hexafluoropropylene copolymer/SiO2 composite membrane, preparation method and application therefor | |
| CN104882609A (en) | Surface modification treatment method for negative electrode graphite in low-temperature lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |